EP0018503A2 - Silyl-Azide, ihre Verwendung zur Herstellung siliziumdioxydverstärkten Gummis und siliciumdioxydverstärkter Gummi - Google Patents

Silyl-Azide, ihre Verwendung zur Herstellung siliziumdioxydverstärkten Gummis und siliciumdioxydverstärkter Gummi Download PDF

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Publication number
EP0018503A2
EP0018503A2 EP80101661A EP80101661A EP0018503A2 EP 0018503 A2 EP0018503 A2 EP 0018503A2 EP 80101661 A EP80101661 A EP 80101661A EP 80101661 A EP80101661 A EP 80101661A EP 0018503 A2 EP0018503 A2 EP 0018503A2
Authority
EP
European Patent Office
Prior art keywords
rubber
trimethoxysilyl
methyl
disulfide
sila
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP80101661A
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English (en)
French (fr)
Other versions
EP0018503A3 (de
Inventor
Albert Wayne Borel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phillips Petroleum Co
Original Assignee
Phillips Petroleum Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Publication of EP0018503A2 publication Critical patent/EP0018503A2/de
Publication of EP0018503A3 publication Critical patent/EP0018503A3/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • This invention relates to certain novel compounds which can be broadly termed to theazides, mercaptans, and disulfides.
  • the invention also relates to the use of certain azides, mercaptans, disulfides and thiosulfenamides as coupling agents or promoters in the production of silica filled rubber compositions.
  • the invention provides, broadly described, as a novel compound or compound, useful as coupling agent or promoter as further described therein, an alkoxy alkyl substituted silyl azide, a silacycloalkyl mercaptan and a bis(silacycloalkyl) disulfide.
  • an alkoxy alkyl substituted silyl azide a silacycloalkyl mercaptan and a bis(silacycloalkyl) disulfide.
  • silica filled rubber composition comprising as a coupling agent or promoter therein at least one of the compounds recited herein and identified as suitable for use as a coupling agent or promoter in the process of the invention also as described herein.
  • a major reinforcing agent for rubber-based products such as tires and extruded and molded goods is carbon black.
  • Carbon black greatly enhances mechanical strength and resistance to abrasion and is thus widely used which explains why the annual worldwide production of carbon black is over 2 billion pounds.
  • Carbon black is produced by the thermal decomposition of hydrocarbons principally oil and natural gas. The increasing demand for other oil or gas- derived petrochemicals plus the decreasing supply of oil and natural gas has prompted searches for a caron black replacement.
  • the best nonblack reinforcing pigments so-far developed are the reinforcing silicas which come the closest to carbon blakc properties of any available material. Cost has heretofore eliminated the use of silica as a serious competitor to carbon black. However, with the advent of new processes some amorphous and fine particle-size silica have emerged which are considered to be economically competitive to carbon black. In addition, promoters or coupling agents have greatly increased the performance level of silica as a rubber reinforcing filler. While full equivalence with carbon black has not yet been achieved, the possibility still exists that better promoters might make silica competitive with carbon black on a performance basis, hence, the need exists for better promoters or coupling agents for silica reinforcing agents.
  • a compound suitable for use as a coupling agent in the silica filled reinforcement of a rubber said compound being represented by one of the following formulas.
  • R and R' are at least one of a linear or branched alkyl or cycloalkyl group having from one to ten carbon atoms and aromatic or substituted aromatic groups having from six to ten carbon atoms
  • x is an integer from 1 to 20 and Y is an azide
  • X is at least one of a halogen and an alkoxy (-OR) group where R in said group and in said formulas A and B is as previously defined and R" is a trivalent hydrocarbon radical having 2 to 10 carbon atoms.
  • a process or method for the improved compounding of a silica filled rubber composition employing as coupling agent or promoter at least one of a compound as already defined and as exemplified later herein and an alkoxy substituted silyl alkyl thiosulfenamide in which the substituted thiosulfenamide group can be represented by the formula wherein each R is the same or different and are as defined herein.
  • silacyclic compounds of this invention corresponding to forumula A.
  • the amount of promoter or coupling agent used in this invention can be broadly from 0.05 to 10 phr (parts of coupling agent per hundred parts of rubber employed). It is preferred to use 0.1 to 3.0 phr.
  • One or more of the coupling agents herein disclosed can be used together. Use of the term “promoter” and/or the term “coupling agent” is not to be taken as limiting the action of the additive(s) of the invention claimed.
  • the elastomer or rubber component of this invention can be any type although it is preferred that the rubber be subject to a sulfur type vulcanization and as such should have some degree of unsaturation.
  • Typical elastomers useful in this invention are for example: natural rubber, homopolymers of conjugated dienes such as butadiene and isoprene, copolymers of conjugated dienes and vinyl aromatics which would include SBR and solution polymerized rubbers, butyl rubber, and nitrile rubber.
  • the polymers can be linear or branched.
  • any type silica can be employed which is considered to have reinforcing properties.
  • this will be silicas with a particle size less than 15 microns and an external surface area of 50 to 250 meters per gram with low porosity (i.e. ⁇ 20 square meters per gram).
  • precipitated grade-silica is preferred over fumed grade silica because of the difference in cost of preparation.
  • Typical examples of some commercial silicas useful in this invention are Hi Sil 233 (PPG Industries), Aerosil (De- gussa) and Cabosil (Cabot Corp.).
  • the recipe used in this invention is considered to be conventional (see U.S. Patent 3,798,196, Examples V to VIII) and thus not critical to the successful operation of the invention, the important feature being the selection of the promoter.
  • the recipe used is shown in Table I.
  • the kettle product from the above distillation was analyzed by gas-liquid chromatography and found to contain 40 wt.% 3-(trimethoxysilyl)-propylazide, 62 wt.% dimer of 3-(trimethoxysilyl)propylazide and 34 wt.% unknowns.
  • the reactor was mechanically shaken at 60 cycles per minute while the contents were irradiated for 8.5 hours after which excess hydrogen sulfide was vented off and the remaining contents distilled in pressence of 0.3 grams elemental sulfur, the sulfur being added to prevent reaction between the mercaptan product and any unreacted CMSCP during distillation.
  • the desired product distilled at 76°C/10 mm to give 113.8 grams (61.9 mole % yield) with 98.2 wt.% purity.
  • a rubber composition was prepared employing a known silicon-based coupling agent, bis(3-triethoxysilylpropyl) tetrasulfide.
  • a known silicon-based coupling agent bis(3-triethoxysilylpropyl) tetrasulfide.
  • three commercially available alkoxy alkyl silanes were also evaluated for comparative purpose. These results listed in Table II are used as controls for the silyl compounds of this invention.
  • Si 69(No.2, Table II) all of the remaining commercial alkoxysilanes (Nos.3,4,5; Table II) were considered unsatisfactory either because of low strenght (300% modulus) or low scorch time.
  • Example VI The rubber composition described in Example VI was again formulated except the coupling agent employed was one of the compounds of. the invention, 3-(trimethoxysilyl)propyl- azide and the corresponding dimer.
  • the results shown in Table III indicate a significant increase in 300 % modulus while maintaining about the same tensile strenght as compared to the control system without a coupling agent (No.1, Table II).
  • Heat build-up ( ⁇ T, °C or hysteresis) is less than the system with no coupling agent which is desirable.
  • Dispersion rate is comparable as well as scorch time.
  • Si 69 No.2, Table II
  • the inventive azide and dimer has comparable properties.
  • Modulus is slightly lower and hysteresis is slightly higher but elongation is better. Most important, however, is improvement in scorch time. With the inventive azides, the scorch time is comparable to the system without a coupling agent (No.1, Table II) and 20 to 40 % better (higher) than the system with a known coupling agent (No.2, Table II).
  • Example VI The rubber composition described in Example VI was again formulated except the coupling agent employed was another one of the compounds of the invention, N,N-Diethyl-3-(trimethoxysilyl) propylthiosulfenamide.
  • the results shown in Table IV indicate this compound exhibits outstanding activity as a coupling agent.
  • the 300 % modulus and tensile strength was too high to measure.
  • the heat build-up ( ⁇ T) was low. Reducing the concentration of the sulfenamide derivative gives good modulus and tensile strenght.
  • the elongation is equal to the control with no coupling agent. Also at the lower concentration, heat build-up is lower and scorch time is close to the control. The lower concentration of the thiosulfenamide derivative also lowers cost. Dispersion appears to be about equal to the control at all concentrations.
  • the principal performance advantage of the thiosulfenamide over the system employing a standard coupling agent (No.2, Table II) is improved scorch time and elongation.
  • Example VI The rubber composition described in Example VI was again formulated except the coupling agent employed was another one of the compounds of the invention, bis(1-chloro-1-methyl-1-sila-3-cyclopentyl) disulfide and the corresponding monomer 1-chloro-1-methyl-3-mercaptosilacyclopen- tane.
  • the results shown in Table V indicate the outstanding properties obtainded when the disulfide derivative (No.3, Table V) of the invention is employed. Modulus is double that of the control system, without a coupling agent, tensile strength about 20 % higher, elongation about 20% lower but still considered good.
  • the heat build-up (A T) is greatly reduced while scorch time is maintained at the same level.
  • the dispersion rate appears about the same.
  • Example VI The rubber composition described in Example VI was again formulated except the coupling agents employed were various other type sulfur containing alkoxy alkyl silane coupling agents. These materials (Nos. 2 to 6, Table VI) were evaluated to demonstrate the unobviousness of the inventive compounds as silica coupling agents, especially those containing sulfur, by showing that not all thiosilyl compounds are particularly useful as coupling agents.
  • the results shown in Table VI generally indicate these comparative thiosilyls (i.e. dithiocarbamates, thiuram disulfides, trithiocarbonates and benzothiazyl sulfides) give higher tensile strengths but lower 300 % modulus. In addition, heat build-up is higher and scorch times are much lower. Also dispersion rates are low indicating poor compatibility.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP80101661A 1979-03-30 1980-03-27 Silyl-Azide, ihre Verwendung zur Herstellung siliziumdioxydverstärkten Gummis und siliciumdioxydverstärkter Gummi Withdrawn EP0018503A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25508 1979-03-30
US06/025,508 US4292234A (en) 1979-03-30 1979-03-30 Silane reinforcing promoters in reinforcement of silica-filled rubbers

Publications (2)

Publication Number Publication Date
EP0018503A2 true EP0018503A2 (de) 1980-11-12
EP0018503A3 EP0018503A3 (de) 1981-01-28

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Family Applications (1)

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EP80101661A Withdrawn EP0018503A3 (de) 1979-03-30 1980-03-27 Silyl-Azide, ihre Verwendung zur Herstellung siliziumdioxydverstärkten Gummis und siliciumdioxydverstärkter Gummi

Country Status (4)

Country Link
US (1) US4292234A (de)
EP (1) EP0018503A3 (de)
JP (1) JPS55131029A (de)
CA (1) CA1150291A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021190766A1 (de) 2020-03-27 2021-09-30 Wacker Chemie Ag Perfluorphenylazid-haltige siloxanoligomermischungen

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3040382A1 (de) * 1980-10-25 1982-05-27 Degussa Ag, 6000 Frankfurt Azidogruppen aufweisende organosiliciumverbindungen, deren herstellung und anwendung
US4401598A (en) * 1980-10-25 1983-08-30 Degussa Aktiengesellschaft Production of organosilicon compounds having azido groups
US4431755A (en) * 1982-07-16 1984-02-14 Standard Oil Company (Indiana) Rubber composition comprising phyllosilicate minerals, silanes, and quaternary ammonium salts
JPH0625284B2 (ja) * 1984-06-19 1994-04-06 株式会社ブリヂストン シリカ配合ゴム組成物
JPS6248743A (ja) * 1985-08-28 1987-03-03 Shin Etsu Chem Co Ltd ゴム組成物
US5085938A (en) * 1989-11-29 1992-02-04 Ppg Industries, Inc. Chemically treated fibers and method of preparing and method of using to reinforce polymers
DE4107664A1 (de) * 1991-03-09 1992-09-10 Basf Lacke & Farben Loesungen von polykondensaten, welche als struktureinheiten n-enthaltende heterocyclische ringsysteme aufweisen, mit verbesserter haftung auf anorganischen substraten
US5489701A (en) * 1994-09-28 1996-02-06 Osi Specialties, Inc. Process for the preparation of silane polysulfides
US5466848A (en) * 1994-09-28 1995-11-14 Osi Specialties, Inc. Process for the preparation of silane polysulfides
KR100404780B1 (ko) * 2000-02-18 2003-11-07 대림산업 주식회사 메탈로센 화합물과 이로부터 제조되는 메탈로센 촉매 및이를 이용한 올레핀의 중합 방법
ATE442407T1 (de) * 2001-06-28 2009-09-15 Michelin Soc Tech Kautschukzusammensetzung für reifen, die ein kupplungsmittel der polythiosulfenamid-gruppe enthält
CN1272370C (zh) * 2001-12-20 2006-08-30 米其林技术公司 包括含有聚硫代次磺酰胺功能团的偶联剂的轮胎橡胶组合物
WO2009044697A1 (ja) * 2007-10-01 2009-04-09 Bridgestone Corporation 有機珪素化合物及びそれを用いたゴム組成物
CN103958592B (zh) 2011-10-24 2015-08-26 普利司通美国轮胎运营有限责任公司 二氧化硅填充的橡胶组合物及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3697551A (en) * 1968-12-31 1972-10-10 Hercules Inc Silane sulfonyl azides
US3813351A (en) * 1968-12-31 1974-05-28 Hercules Inc Priming composition
GB1377214A (en) * 1972-07-12 1974-12-11 Dow Corning Ltd Organosilicon compounds
DE2704506A1 (de) * 1976-02-06 1977-08-11 Malaysian Rubber Producers Substituierte azosilane, verfahren zu ihrer herstellung und ihre verwendung

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3655713A (en) * 1970-07-13 1972-04-11 Dow Corning Silacyclopentane thiols and thiolates
US3947436A (en) * 1970-07-18 1976-03-30 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Sulfur containing organo-organooxysilane
AR207457A1 (es) * 1974-01-10 1976-10-08 Degussa Mezcla adhesiva de caucho para mejorar la adhesividad de mezclas vulcanizables de textiles o tejidos metalicos despues del vulcanizado
CA1046681A (en) * 1974-06-25 1979-01-16 Union Carbide Corporation Mercapto-silane coupler-inorganic powder mixtures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3697551A (en) * 1968-12-31 1972-10-10 Hercules Inc Silane sulfonyl azides
US3813351A (en) * 1968-12-31 1974-05-28 Hercules Inc Priming composition
GB1377214A (en) * 1972-07-12 1974-12-11 Dow Corning Ltd Organosilicon compounds
DE2704506A1 (de) * 1976-02-06 1977-08-11 Malaysian Rubber Producers Substituierte azosilane, verfahren zu ihrer herstellung und ihre verwendung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021190766A1 (de) 2020-03-27 2021-09-30 Wacker Chemie Ag Perfluorphenylazid-haltige siloxanoligomermischungen

Also Published As

Publication number Publication date
JPS55131029A (en) 1980-10-11
EP0018503A3 (de) 1981-01-28
CA1150291A (en) 1983-07-19
US4292234A (en) 1981-09-29

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Inventor name: BOREL, ALBERT WAYNE